(+-)-methyl-[2exo]norbornyl ether | 10395-53-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (+-)-methyl-[2exo]norbornyl ether
• 英文别名: exo-2-methoxybicyclo[2.2.1]heptane；exo-2-norbornyl methyl ether；exo-norbornyl methyl ether；exo-2-methoxynorbornane；(+/-)-methyl-[2exo]norbornyl ether；(+/-)-Methyl-[2exo]norbornyl-aether；(1R,2R,4S)-2-methoxybicyclo[2.2.1]heptane
• CAS: 10395-53-6
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: WMYWLMCIILHCPB-XLPZGREQSA-N

物化性质

• 沸点：
  158.6±8.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+-)-methyl-[2exo]norbornyl ether 在 HOF* CH₃CN 、 sodium fluoride 作用下， 以 氯仿 、 水 、 乙腈 为溶剂， 以80%的产率得到降樟脑
  参考文献：
  名称：

  Oxidative Cleavage of Methyl Ethers Using the HOF.cntdot.CH3CN Complex

  摘要：

  HOF . CH3CN complex, made easily by bubbling fluorine diluted with nitrogen through aqueous acetonitrile, proved to be a suitable oxidizer for various methyl ethers. Secondary ethers are oxidized to ketones and even to lactones via Baeyer-Villiger type of oxidation. The reaction is ionic, and the reagent's electrophilic oxygen attacks the relatively electron rich C-H bend alpha to the ether moiety. It was found that the more sterically hindered is the C-H bond in question, the slower the reaction. In cases where this bond is an electron poor one as in benzoin methyl ether (9), no reaction takes place. When labeled (HOF)-O-18 . CH3CN is used on a O-16 methyl ether, the resulting ketone possesses only the heavier oxygen isotope. Primary methyl ethers are somewhat slower to react, but they too were oxidized in very good yields to acids via the corresponding aldehydes.

  DOI：

  10.1021/jo00130a029
• 作为产物：
  描述：

  降莰烷 在 三氯化铝 、 magnesium oxide 、 正戊烷 作用下， 生成 (+-)-methyl-[2exo]norbornyl ether
  参考文献：
  名称：

  Treatment of bicycloparaffins

  摘要：

  公开号：

  US02448156A1

文献信息

• THE MECHANISMS OF OXYMERCURATION
  作者：M. J. Abercrombie、Alan Rodgman、K. R. Bharucha、George F Wright

  DOI：10.1139/v59-196

  日期：1959.8.1

  The oxymercuration of norbornenes has been found to be acid-catalyzed, and to give oxymercurials which have a higher dipole moment and greater stability toward deoxymercuration than do their diastereomers in which the configuration of the mercuri linkage has been inverted. Since these properties can be correlated with those of the oxymercurials from norbornenedicarboxylic acids (partly published heretofore

  已发现降冰片烯的氧汞化是酸催化的，并且产生的氧汞比它们的非对映异构体具有更高的偶极矩和更高的脱氧汞稳定性，其中汞键的构型已被反转。由于这些性质可以与来自降冰片烯二羧酸的氧汞（此前部分公开并在本报告中详细阐述）的那些构型相关，其构型是已知的，因此来自降冰片烯的氧汞的构型是↑↓（反式）。但是这些构型必须与来自环己烯、环戊烯、α-萜品醇和地球异构二苯乙烯的氧汞的构型相反，其形成不是酸催化的，其偶极矩低于非对映异构体的偶极矩，相对于汞键倒转。这些氧汞的构型必须是↓↓（顺式）并且它们的形成机制必须不同于酸催化...
• Facile Addition of Poorly Nucleophilic Alcohols to Unactivated Alkenes
  作者：Dale F. Shellhamer

  DOI：10.1055/s-1997-1313

  日期：1997.9

  Electronegative substituted (polyfluorinated and polynitroaliphatic), poorly nucleophilic alcohols are efficiently added to model alkenes norbornene, cyclohexene, hex-1-ene, and hex-3-ene under mild conditions by the use of boron trifluoride-diethyl ether complex catalyst, forming the corresponding ethers.

  电负性取代的（含氟和含硝环烷基的）、弱亲核性的醇类在温和条件下，通过使用三氟化硼二乙醚络合物催化剂，有效地加成到模型烯烃降樟烯、环己烯、己-1-烯和己-3-烯中，形成相应的醚。
• Addition reactions of alkenes with electronegatively substituted alcohols in the presence of xenon difluoride
  作者：Melvin L. Druelinger、Dale F. Shellhamer、Robert D. Chapman、Scott A. Shackelford、Maurice E. Riner、Steven L. Carter、Ryan P. Callahan、Cameron R. Youngstrom

  DOI：10.1039/a604677k

  日期：——

  The electrophilic reactivity of proposed alkoxyxenon fluoride (ROXeF) intermediates based on electronegatively substituted (polyfluorinated and polynitroaliphatic) alcohols has been characterized with model alkenes norbornene, 2-methylpent-1-ene and hex-1-ene. The alkoxyxenon fluorides can react as positive oxygen electrophiles—initially incorporating alkoxy substituents—or as apparent fluorine electrophiles—resulting in initial fluorine incorporation—depending on conditions. Efficient simple addition of poorly nucleophilic alcohols to norbornene was observed in certain systems. Selectivity between the various reaction paths (simple fluorination, alkoxyfluorination or alcohol addition) was observed to be a sensitive function of various reaction conditions, especially solvent, temperature and catalyst.

  根据电负性取代的（多氟化和多硝基脂肪族）醇，提出的醇氧氟氙（ROXeF）中间体的电亲反应性已通过模型烯烃如内苯、2-甲基戊-1-烯和己-1-烯进行表征。这些醇氧氟氙可作为正氧电亲体反应——最初引入醇氧取代基——或作为表观氟电亲体反应——导致初始氟的引入——具体取决于反应条件。在某些体系中，观察到欠亲核醇与内苯之间的高效简单加成。不同反应路径（简单氟化、醇氧氟化或醇加成）之间的选择性被认为是各种反应条件的敏感函数，特别是溶剂、温度和催化剂。
• Electrochemical Syntheses. IV. The Homolytic Methoxylation and Ethoxylation of Olefins by the Anodic Oxidation of Methanol and Ethanol
  作者：Tadao Inoue、Kikuhiko Koyama、Toru Matsuoka、Shigeru Tsutsumi

  DOI：10.1246/bcsj.40.162

  日期：1967.1

  The electrochemical oxidation of methanol and ethanol in the presence of trans-stilbene, cis-stilbene, norbornene, and styrene has been studied. The major gaseous and nongaseous products have been identified and determined, and the corresponding dimethoxylated derivatives and diethoxylated derivatives have been obtained in fairly high yields. The main path by which these products may have arisen has

  已经研究了在反式二苯乙烯、顺二苯乙烯、降冰片烯和苯乙烯存在下甲醇和乙醇的电化学氧化。主要的气态和非气态产物已被鉴定和测定，相应的二甲氧基化衍生物和二乙氧基化衍生物已以相当高的收率获得。已经讨论了这些产物可能产生的主要途径，并且讨论了将甲氧基自由基加成到二苯乙烯的立体化学。已经特别关注主要产物产生于中间自由基阳极氧化成碳正离子的可能性。
• The 2-Norbornyl Cation via the Fragmentations of <i>exo</i>- and <i>endo</i>-2-Norbornyloxychlorocarbenes:  Distinction without Much Difference
  作者：Robert A. Moss、Fengmei Zheng、Ronald R. Sauers、John P. Toscano

  DOI：10.1021/ja010598q

  日期：2001.8.1

  exo- and endo-2-norbornyloxychlorocarbenes (7) were generated photochemically from the corresponding diazirines (6). Both carbenes fragmented to [2-norbornyl cation (carbon monoxide) chloride] ion pairs in MeCN or 1,2-dichloroethane solutions. Products included exo-norbornyl chloride (8), endo-norbornyl chloride (9), norbornene (10), and nortricyclene (11). Fragmentation activation energies were very

  外型和内型 2-降冰片基氧基氯卡宾 (7) 是从相应的二氮嗪 (6) 光化学生成的。两种卡宾在 MeCN 或 1,2-二氯乙烷溶液中均裂解为 [2-降冰片基阳离子（一氧化碳）氯化物] 离子对。产品包括外型降冰片酰氯 (8)、内型降冰片酰氯 (9)、降冰片烯 (10) 和降三环烯 (11)。碎裂活化能非常低（< 大约 4 kcal/mol），因此，exo-7 和 end-7 的（激光闪光光解）碎裂速率常数基本相同（大约 5 x 10(5) s (-1) 在 MeCN 中）。由于离子对内的氯返回，exo-7 和endo-7 的产物分布不同，更多的内氯由内卡宾形成：MeCN 中 8/9 的产物比大约是 exo-7 的 41，但只有4.6 来自endo-7。降冰片烯由质子转移到离子对内的 Cl(-) 形成，在两种情况下都是主要产物（44% 来自 exo-7，62% 来自endo-7）。在 MeOH/MeCN